US4910128A - Silver halide color photographic material - Google Patents

Silver halide color photographic material Download PDF

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Publication number
US4910128A
US4910128A US07/245,941 US24594188A US4910128A US 4910128 A US4910128 A US 4910128A US 24594188 A US24594188 A US 24594188A US 4910128 A US4910128 A US 4910128A
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group
silver halide
photographic material
color photographic
halide color
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Takayoshi Kamio
Katsuyoshi Yamakawa
Hidetoshi Kobayashi
Isamu Itoh
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Assigned to FUJI PHOTO FILM CO., LTD. reassignment FUJI PHOTO FILM CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: ITOH, ISAMU, KAMIO, TAKAYOSHI, KOBAYASHI, HIDETOSHI, YAMAKAWA, KATSUYOSHI
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/305—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers
    • G03C7/30511—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers characterised by the releasing group
    • G03C7/30517—2-equivalent couplers, i.e. with a substitution on the coupling site being compulsory with the exception of halogen-substitution
    • G03C7/30523—Phenols or naphtols couplers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/78—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C07C217/80—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings
    • C07C217/82—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring
    • C07C217/90—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring the oxygen atom of at least one of the etherified hydroxy groups being further bound to a carbon atom of a six-membered aromatic ring, e.g. amino-diphenylethers

Definitions

  • This invention relates to cyan-dye-forming couplers (also referred to herein more simply as "cyan couplers”), and more specifically, it relates to silver halide color photographic materials containing novel cyan couplers having a particular aryloxy group at the 4-position removable by coupling with an oxidized form of an aromatic primary amine color developing agent, and other particular substituents at the 2-position and the 5-position.
  • the color forming coupler is either added to a developing solution or included in a photosensitive photographic emulsion layer or other color image forming layer, and by reacting with an oxidized form of a color developer formed by development, a nondiffusing dye is formed.
  • Coupler position The reaction of the coupler and the color developer takes place at the active site of the coupler (referred to as the "coupling position"), and a coupler having only hydrogen atoms on this active site is a four-equivalent coupler, i.e., stoichiometrically requiring 4 moles of silver halide having developing nuclei for forming 1 mole of dye.
  • a coupler having a removable group as an anion at the active site is a two-equivalent coupler, i.e., a coupler which stoichiometrically requires only 2 moles of silver halide developing nuclei for forming 1 mole of dye.
  • the amount of the silver halide in the photosensitive layer may be lowered and hence the thickness thereof may be reduced, it is possible to shorten the time required for processing the photosensitive material, and furthermore, sharpness of the formed color image in enhanced.
  • phenol type couplers and naphthol type couplers known as cyan color forming couplers
  • OPI Japanese Patent Application
  • 65134/81, 204,543/82, 204,544/82, 204,545/82, 33249/83, 33250/83 etc. the term "OPI” as used herein refers to a "published unexamined Japanese patent application"
  • phenol type couplers having a phenylureido group at the 2-position and further an acylamino group at the 5-position are superior to the other cyan couplers in light fastness of the color images formed by color development.
  • one object of this invention is to provide silver halide photographic materials utilizing novel phenolic cyan couplers having excellent heat and light fastness properties in the color developed image and having remarkably improved color developing properties and dispersibility.
  • Another object of this invention is to present couplers with which there is substantially no reduction in the developed color density even when treated with a bleaching solution having a weak oxidizing power or an exhausted bleaching solution.
  • R 1 represents a ballast group imparting diffusion fastness to the coupler of formula (I) and a cyan dye formed from said coupler, and preferably represents an aliphatic group, an aromatic group, or a heterocyclic group, each having from 4 to 32 carbon atoms
  • X represents a hydrogen atom or a gorup represented by --R, --OR, --SR, ##STR6## --COR, --COOR, --SO 2 R, --SO 2 OR, ##STR7## or --OCOR
  • Y represents a halogen atom, a cyano group, a trifluoromethyl group, a nitro group, or a group represented by --R, --OR, --SR, --COR, --COOR, --SO 2 R, --SO 2 OR, ##STR8##
  • m and n each represents an aliphatic group, an aromatic group, or a heterocyclic group, each having from 4 to 32 carbon atoms
  • X represents a hydrogen atom or a gorup represented
  • the aforesaid aliphatic group means a straight-chain or branched-chain alkyl, alkenyl, or a alkynyl group, which may optionally be substituted.
  • aromatic group means a substituted or unsubstituted aryl group
  • heterocyclic group means a substituted or unsubstituted monocyclic or fused hetero ring.
  • R 1 preferably represents a substituted or unsubstituted alkyl or aryl group, and especially preferably a tertiary alkyl group having from 4 to 32 carbon atoms or a group represented by formula (II) ##STR9## wherein Z represents an oxygen atom, a sulfur atom, --SO--, or --SO 2 ; k represents an integer of 0 to 4, and l represents 0 or 1, and when k is 2 or higher, the R 3 are the same or different; R 2 represents a straight-chain or branched-chain alkylene group having from 1 to 24 carbon atoms; and R 3 represents a monovalent group, for example, a hydrogen atom, a halogen atom (preferably cholorine or bromine), an alkyl group (preferably a straight-chain or branched-chain alkyl group having from 1 to 20 carbon atoms, e.g., methyl, tert-butyl, ter
  • X preferably represents a halogen atom or a substituted or unsubstituted alkyl, aryl, alkoxy, alkoxycarbonyl, or carbonamido group; more preferably one of X represents an alkyl or aryl group present at the para-position with respect to the oxygen atom attached to the active site for the coupling reaction.
  • the total number of carbon atoms of the substituent (X) m is preferably from 4 to 32, and more preferably from 8 to 32.
  • alkyl group examples include methyl, ethyl, isopropyl, tert-butyl, tert-amyl, tert-hexyl, tert-octyl, tert-decyl, tert-pentadecyl, cyclopentyl, cyclohexyl, pentadecyl, allyl, hexadecyl, benzyl, sec-dodecyl, sec-octodecyl, etc.
  • Examples of the aryl group include phenyl, 2-methylphenyl, 4-methoxyphenyl, etc.; examples of the alkoxy group include methoxy, ethoxy, dodecyloxy, methoxyethoxy, etc.; examples of the alkoxycarbonyl group include methoxycarbonyl, dodecyloxycarbony, etc.; and examples of the carbonamido group include acetamido, tetradecanamido, etc.
  • Examples of the arylsulfonyl group include benzenesulfonyl, toluenesulfonyl, etc.; examples of the alkylsulfonyl group include methanesulfony, propanesulfonyl, butanesulfonyl, benzylsulfonyl, tryfluoromethanesulfony, etc.; examples of the sulfonamido group include methanesulfonamido, toluenesulfonamido, triflouromethanesulfonamido, etc.; examples of the sulfamoyl group include sulfamoyl, diethylsulfamoyl, methylsulfamoyl, etc.; examples of the carbamoyl group include carbamoyl, dimethylcarbamoyl, methoxyethylcarbamyl, etc.; and examples of the alk
  • the compounds of formula (I) are couplers preferably characterized by having a substituted phenylureido group at the 2-position of the phenol and also a ballasting carbonamido group having from 8 to 32 carbon atoms in total at the 5-position, and further having a substituted phenyloxy group having 4 or more carbon atoms in total in the substituent at the 4-position as a removable group upon formation of a cyan color image by a coupling reaction with a color developer in the oxidized form.
  • examples of the phenolic cyan couplers having a substituted phenylureido group at the 2-position, an aryloxy group at the 4-position and a carbonamido group at the 5-position there have been disclosed, for example, examples of a phenoxy group at the 4-position in Japanese Patent Application (OPI) No. 65134/81, examples of a 3-chlorophenoxy group and a 4-methoxyphenoxy group in the amendment of Japanese Patent Application (OPI) No. 121,330/84examples of a 3-methylphenoxy group and a 4-methoxyphenyl group at the 4-position in the amendment of Japanese Patent Application (OPI) No.
  • the couplers of this invention are characterized by having a highly lipophilic aryloxy group having 4 or more carbon atoms in total in the substituent at the 4-position, whereby the objects to be solved by this invention have thus been achieved. That is, they are excellent in solubility in both low boiling and high boiling organic solvents and can prevent coating problems.
  • the developed color density and sensitivity are high and the color developing properties are excellent, it is possible to reduce the content of the silver halide.
  • the dyes obtained from the couplers of this invention not only exhibit excellent fastness to light and heat, but also have the feature that there is no substantial reduction in the developed color density even when treated with a bleaching solution having a weak oxidizing power or an exhausted bleaching solution, and therefore they are suitable for rapid processing treatment or treatment not using a coupling accelerator such as benzyl alcohol, etc., as well as for normal processing treatment. These features have been surprising beyond expectation.
  • Preferred phenolic cyan couplers of this invention are illustrated below, but such should not be considered as limiting this invention.
  • the cyan dye forming couplers of this invention may be easily synthesized according to the following general synthetic process. ##STR32##
  • R 1 , X, Y, m and n are as defined above for formula (I).
  • a specific synthesis example is given below.
  • the amount of the couplers of this invention added is generally from 1 ⁇ 10 -3 mole to 7 ⁇ 10 -1 mole, and preferably from 1 ⁇ 10 -2 mole to 5 ⁇ 10 -1 mole, per mole of silver in a silver halide emulsion layer constituting a photosensitive layer of the material.
  • the couplers of this inventions and couplers used in combination with this invention described hereinafter may be incorporated into photosensitive materials by various known dispersing methods, and representative examples thereof include a solid dispersing method, and alkali dispersing method, preferably a latex dispersing method, more preferably an oil-in-water dispersing method, etc.
  • the coupler may be dissolved in either a single solvent or a mixed solvent of a high boiling organic solvent having a boiling point of 175° C.
  • a low boiling solvent i.e., a so-called co-solvent
  • a so-called co-solvent finely dispersed in water or an aqueous solvent such as a gelatin aqueous solution in the presence of a surfactant.
  • a surfactant examples of the high boiling organic solvents are described in U.S. Pat. No. 2,322,027, etc. Dispersing may be accompanied by phase inversion, and, if needed, the co-solvent may be removed or reduced by distillation, noodle washing with water, ultrafiltration, etc., before use in coating.
  • the high boiling organic solvent include phathalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, didodecyl phthalate, etc.) esters of phosphoric acid or phosphonic acid (triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl-diphenyl phosphate, tri-2-ethylhexyl phosphate, tridecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexyl-phenyl phosphonate, etc.), benzoic acid esters (2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl p-hydroxybenzoate, etc.), amides (diethyldodecanamide, N-tetradecyl est
  • an organic solvent having a boiling point of from about 30° to 160° C. may be used, and representative examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide, etc.
  • color couplers means compounds capable of forming dyes by reacting an oxidized form of an aromatic primary amine developing agent.
  • useful color couplers include naphthol or phenol type compounds, pyrazolone or pyrazoloazole type compounds and open ring or heterocyclic ketomethylene compounds.
  • Specific examples of the cyan, magenta and yellow couplers which may be used in this invention are described in the patent cited in Research Disclosure, RD Nos. 17643 (Dec., 1978) VII-D and 18717 (Nov., 1979).
  • couplers preferably have a ballast group or have been polymerized, and hence are nondiffusing,
  • the coupling position is preferably substituted by a removable group rather than a hydrogen atom. It is also possible to use a coupler imparting appropriate diffusing properties to the resulting developed dye, a colored coupler, a colorless coupler, or a coupler releasing a development retarder or a development accelerator upon the coupling reaction.
  • yellow couplers which may be used in this invention
  • oil protected type acylacetamide type couplers may be mentioned as representative examples. Specific examples thereof are described in U.S. Pat. Nos. 2,407,210, 2,875,057, 3,265,506, etc.
  • Two equivalent yellow couplers may preferably be used in this invention, and representative examples thereof are oxygen atom removing type yellow couplers as described in U.S. Pat. Nos. 3,408,194, 3,447,928, 3,933,501, 4,401,752, etc., or nitrogen atom removing type yellow couplers as described in Japanese Patent Publication No. 10739/83, U.S. Pat. Nos. 4,022,620, 4,326,024, Research Disclosure, RD No.
  • ⁇ -Pivaloylacetanilide type couplers are characterized by fastness of the developed dye, while ⁇ -benzoylacetonitrile type couplers are characterized by good color developing properties.
  • magenta couplers which may be used in this invention, there may be mentioned couplers of oil protected type indazolone or cyanoacetyl type, preferably 5-pyrazolone type and pyrazoloazole type such as pyrazolotriazoles, etc.
  • 5-pyrazolone type couplers those having an arylamino group or an acylamino group substituted at the 3-position are preferred from viewpoints of the hue of the developed dye and the developing speed. Representative examples thereof are described in U.S. Pat. Nos. 2,311,082, 2,343,703, 2,600,788, 2,908,573, 3,062,653, 3,152,896, 3,936,015, etc.
  • 5-pyrazolone type couplers Two-equivalent 5-pyrazolone type couplers are preferred, and as the leaving group, a nitrogen atom leaving group as described in U.S. Pat. No. 4,310,619 or an arylthio group as described in U.S. Pat. No. 4,351,897 is preferred.
  • 5-Pyrazolone type couplers having a ballast group as described in European Pat. No. 73,636 have high color developing reactivity.
  • pyrazoloazole type couplers examples include pyrazolobenzimidazoles described in U.S. Pat. No. 3,369,897, preferably pyrazolo[5,1-c][1,2,4]triazoles as described in U.S. Pat. No. 3,725,067, pyrazolotetrazoles as described in Research Disclosure, RD No. 24220 (June, 1984), and pyrazolopyrazoles as described in Research Disclosure, RD No. 24230 (June, 1984).
  • Imidazopyrazoles described in Japanese Patent Application No. 23434/83 and pyrazolo[1,5-b][1,2,4]triazoles described in Japanese Patent Application No. 45512/83 are most preferred in view of low yellow secondary absorption of the developed dye and light fastness.
  • cyan couplers which may be used in combination with the couplers of this invention, there may be mentioned oil protected type naphthol type and phenol type couplers, and representative examples thereof include naphthol type couplers as described in U.S. Pat. No. 2,474,293, preferably oxygen atom removing type high active two equivalent naphthol type couplers described in U.S. Pat. Nos. 4,052,212, 4,146,396, 4,228,233, and 4,296,200. Specific examples of the phenol type couplers are described in U.S. Pat. Nos. 2,369,929, 2,423,730, 2,772,162, 2,895,826, etc.
  • Cyan couplers fast i.e., resistant to heat, moisture, and temperature are preferably used in this invention, and typical examples thereof include phenol type cyan couplers as described in U.S. Pat. No. 3,772,002, 2,5-diacylamino substituted phenol type couplers as described in U.S. Pat. Nos. 2,772,162, 3,758,308, 4,126,396, 4,334,011, 4,327,173, German OLS No. 3,329,729, Japanese Patent Application No. 42671/83, etc., phenol type couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position, as described in U.S. Pat. Nos. 3,446,622, 4,333,999, 4,451,559, 4,427,767, etc., and the like.
  • couplers may be used, in order to satisfy the characteristics required of the photosensitive materials, in such a way that two or more thereof are incorporated in the same layer, or that the same compound is added to two or more different layers.
  • a colored coupler in combination in color photosensitive materials for photography.
  • Representative examples thereof include yellow-colored magenta couplers as described in U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 39413/82, etc., magenta-colored cyan couplers as described in U.S. Pat. Nos. 4,004,929, 4,138,258, British Pat. No. 1,146,368, etc.
  • a black-dye-forming coupler used e.g., for saving silver in photosensitive materials for X-rays may also be used in this invention. Specific examples thereof are described in U.S. Pat. No. 4,126,461, British Pat. No. 2,102,136, etc.
  • color couplers may form polymers, i.e., dimers or higher polymers.
  • Representative examples of polymerized couplers are described in U.S. Pat. Nos. 3,451,820 and 4,080,211.
  • Specific examples of polymerized magenta couplers are described in British Pat. No. 2,102,173 and U.S. Pat. No. 4,367,282.
  • a developed dye diffusing coupler it is possible to improve graininess (i.e., to decrease graininess) by using in combination a developed dye diffusing coupler.
  • a coupler may be found, e.g., in the magenta couplers described in U.S. Pat. No. 4,336,237 and British Pat. No. 2,125,570, and specific examples of the yellow, magenta, and cyan couplers are described in European Pat. No. 96,873 and German OLS No. 3,324,533.
  • This invention may be used in general silver halide color photosensitive materials, such as color negative films, color paper, color positive films, color reversal films for slides, color reversal films for motion pictures, color reversal films for TV, etc. Especially, they are suitably applied to color negative films and various color reversal films for which high sensitivity and high image quality are required. Further, they may also be used in color paper.
  • the silver halide color photosensitive materials of this invention preferably utilize a UV absorber for enhancing light fastness.
  • a UV absorber for enhancing light fastness.
  • another protective layer may be coated as the outermost layer.
  • This protective layer may contain a matting agent having particles (diameter not limited), etc.
  • the aforesaid UV absorber may be dissolved in either a single solvent or a mixed solvent of a high boiling organic solvent and a low boiling organic solvent and dispersed in a hydrophilic colloid. While the amount of the high boiling organic solvent and the UV absorber is not particularly restricted, it is generally suitable to use the high boiling organic solvent in the range of from 0 to 300% based on the weight of the UV absorber. Compounds which are liquid at normal temperature are preferably used, either alone or in combination.
  • the use of the aforesaid benzotraizole type UV absorber in combination with the combination of the couplers of this invention improves storability, especially light fastness, of developed dye images, especially cyan images.
  • This UV absorber and the cyan coupler may be co-emulsified.
  • organic or metal complex type discoloration inhibitors may be used therewith.
  • organic discoloration inhibitors include hydroquinones, gallic acid derivatives, p-alkoxyphenols, p-oxyphenols, etc., and for dye image stabilizers, stain inhibitors or antioxidants, patents are cited in Research Disclosure, RD No. 17643, VII, Section I or J. Metal complex type discoloration inhibitors are described in Research Disclosure, Rd No. 15162, etc.
  • various silver halides may be used, e.g., silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc.
  • Silver iodobromide containing from 2 to 20 mole % silver iodide and silver chlorobromide containing from 10 to 15 mole % of silver bromide are preferred.
  • crystal form, crystal structure, grain diameter, grain diameter distribution, etc., of the silver halide grains are not restriction on the crystal form, crystal structure, grain diameter, grain diameter distribution, etc., of the silver halide grains.
  • the crystals of the silver halide may be normal or twin, and may be in the form of hexahedron, octahedron, or tetradecahedron.
  • the crystal structure may be uniform or of different compositions between the inside and outside, or may be in a stratified structure, of may be of epitaxially joined silver halides having different compositions, or may be composed of a mixture of grains of various crystal forms. Further, they may be either that forming the latent image mainly on the grain surface or that forming it inside.
  • the grain diameter of the silver halide may be as small as 0.1 micron or less, or as large as 3 mircons, based on the projected area diameter, and its emulsion may be either a single dispersed emulsion having narrow distribution or a multi-dispersed emulsion having large distribution.
  • silver halide grains may be produced by known processes conventionally employed in the art.
  • the above-described silver halide emulsions may be sensitized by conventional chemical sensitization, i.e., sulfur sensitization, noble metal sensitization, or a combination thereof. Further, the silver halide emulsions of this invention may be imparted with color sensitivity to a desired photosensitive wavelength region by using a sensitizing dye.
  • the dye advantageously used in this invention include methine dyes and styryl dyes as cyanine, hemicyanine, rhodacyanine, merocyanine, oxonol, hemioxonol, etc., and they must be used either singly or in combinations of two or more thereof.
  • a transparent base of, e.g., polyethylene terephthalate, cellulose triacetate, etc., or a reflecting base described hereinlater may be used.
  • the reflecting base is preferred, and examples include baryta paper, polyethylene-coated paper, polypropylene type synthetic paper, a transparent base either provided with a reflecting layer or using in combination a reflecting body, for example, glass plates, polyester films of, e.g., polyethylene terephthalate, cellulose triacetate, cellulose nitrate, etc., polyamide films, polycarbonate films, polystyrene films, etc.
  • These bases may be appropriately chosen according to the intended purpose.
  • the blue-sensitive, green-sensitive, and red-sensitive emulsions are those spectrally sensitized by methine dyes to render color sensitivity, respectively.
  • the dye used include cyanine dyes, merocyanine dyes, compound cyanine dyes, compound merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes.
  • Particularly useful dyes are cyanine dyes, merocyanine dyes, and compound merocyanine dyes.
  • the color photographic material of this invention may incorporate, in addition to the above-described constituting layers, auxiliary layers such as a subbing layer, an intermediate layer, a protective layer, etc. Further, as needed, a second UV absorbing layer may be provided between the red-sensitive silver halide emulsion layer and the green-sensitive silver halide emulsion layer. In this UV absorbing layer, although it is preferred to use the above-described UV absorbers, other known UV absorbers may also be used.
  • gelatin is advantageous as the binder or the protective colloid for the photographic emulsion, other hydrophillic colloids may also be used.
  • proteins may be used, such as gelatin derivatives, graft polymers of gelatin and other polymers, albumin, casein, etc.; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfate esters, etc., sugar derivatives such as sodium alginate, starch derivatives; and various hydrophilic polymeric substances such as homopolymers and copolymers, e.g., polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc.
  • polyvinyl alcohol polyvinyl alcohol partial acetal
  • poly-N-vinylpyrrolidone polyacrylic acid
  • polymethacrylic acid polyacrylamide
  • polyvinylimidazole polyvinylpyrazole
  • Gelatins that may be used include lime-treated gelatin, acid-treated gelatin, or enzyme-treated gelatin as described in Bull. Soc. Sci. Phot. Japan, No. 16, p. 30 (1966), and further a hydrolysate or enzymatic hydrolysate of gelatin may also be used.
  • the hydrophilic colloid layers of the photographic emulsion layers, etc. may further contain brigthening agents of stilbene type, triazine type, oxazole type, coumarine type, etc. They may be water-soluble, or may be water-insoluble and used in the form of a dispersion.
  • fluorescent brighteners are described in U.S. Pat. Nos. 2,632,701, 3,269,840 and 3,359,102, British Pat. Nos. 852,075 and 1,319,763, description under "Brighteners" of p. 24, left column, lines 9 to 36 of Research Disclosure, Vol. 176, RD No. 17643 (published in December, 1978), etc.
  • dyestuffs, UV absorbers, etc. are contained in the hydrophilic colloid layers, they may also be mordanted by a cationic polymer, etc.
  • a cationic polymer etc.
  • polymers described in British Pat. No. 685,475, U.S. Pat. Nos. 2,675,316, 2,839,401, 2,882,156, 3,048,487, 3,184,309 and 3,445,231, German OLS No. 1,914,362, Japanese Patent Application (OPI) Nos. 47642/75, 71332/75, etc. may be used.
  • the photosensitive materials of this invention may contain, as a fogging inhibitor, hydroquinone derivatives, aminophenyl derivatives, gallic acid derivatives, ascorbic acid derivatives, etc., and specific examples thereof are described in U.S. Pat. Nos. 2,360,290, 2,336,327, 2,403,721, 2,418,613, 2,675,314, 2,701,197, 2,704,713, 2,728,659, 2,732,300 and 2,735,765, Japanese Patent Application (OPI) Nos. 92988/75, 92989/75, 93928/75, 110,337/75, 146,235/77, Japanese Patent Publication No. 23813/75, etc.
  • OPI Japanese Patent Application
  • the color photographic material of this invention may contain, in addition to those described above, various photographic additives known in this art, for example, stabilizers, fogging inhibitors, surfactants, couplers other than those of this invention, filter dyestuffs, irradiation-preventing dyestuffs, developing agents, etc., as needed, and examples thereof are described in Research Disclosure, RD No. 17643, supra.
  • a finely divided silver halide emulsion substantially free from photosensitivity e.g., silver chloride, silver bromide, silver chlorobromide emulsions, etc. having an average grain size of 0.20 ⁇ or less
  • photosensitivity e.g., silver chloride, silver bromide, silver chlorobromide emulsions, etc. having an average grain size of 0.20 ⁇ or less
  • the color developing solution which may be used in this invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as an active ingredient.
  • the color developing agent include 4-amino-N,N-diethylaniline, 3-methyl-4-amino-N,N-diethylaniline, 4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline, 3-methyl-4-amino-4-ethyl- ⁇ -hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methanesulfonamidoethylaniline, 4-amino-3-methyl-N-ethyl-N- ⁇ -methoxyethylaniline, etc.
  • the color developing solution may contain pH buffers such as sulfites, borates, phosphates, etc., of alkali metals, development retarders or fogging inhibitors such as bromide, iodide, or organic fogging inhibitors, etc.
  • it may further contain, as needed, hard water softeners, preservatives such as hydroxylamine, organic solvents such as benzyl alcohol, diethylene glycol, etc., developing accelerators such as polyethylene glycol, quaternary ammonium salts, amines, etc., dye forming couplers, competing couplers, fogging agents such as sodium boron hydride, etc., auxiliary developers such as 1-phenyl-3-pyrazolidone, thickeners, polycarboxylic acid type chelating agents described in U.S. Pat. No. 4,083,723, antioxidants described in German OLS No. 2,662,950, etc.
  • hard water softeners preservatives such as hydroxylamine, organic solvents such as benzyl alcohol, diethylene glycol, etc.
  • developing accelerators such as polyethylene glycol, quaternary ammonium salts, amines, etc.
  • dye forming couplers such as sodium boron hydride, etc.
  • auxiliary developers such as 1-phen
  • the photographic emulsion layers of the color developing solution are usually bleached.
  • the bleaching process may be conducted simultaneously with the fixing process or may be conducted separately.
  • compounds of polyvalent metals such as iron (III), cobalt (III), chromium (VI), copper (II), etc., peroxo acids, quinones, nitroso compounds, etc. may be used.
  • bleaching agent examples include ferricyanide compounds, bichromates, organic complexes of iron (III) or cobalt (III); aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid, etc.; complexes of organic acids such as citric acid, tartaric acid, malic acid, etc.; persulfates; permanganates; nitrosophenol; etc.
  • potassium ferricyanide, sodium iron (III) ethylenediaminetetraacetate and ammonium iron (III) ethylenediaminetetraacetate are particularly useful.
  • the iron (III) ethylenediaminetetraacetate complexes are useful in both separate bleaching bath and combined bleaching and fixing bath.
  • the color development or the bleaching and fixing process may optionally be followed by washing with water.
  • the color development is generally effected at a temperature of from 18° to 55° C., preferably at 30° C. or higher, and particularly preferably at 35° C. or higher.
  • the time required for the development is in the range of from about 3.5 minutes to about one minute, the shorter time being preferred.
  • the solution is preferably replenished in the case of continuous processing, and a replenisher is supplied in an amount not greater than 330 cc, and preferably not greater than 100 cc, per square meter of the area to be processed.
  • the benzyl alcohol content in the developing solution is preferably not greater than 5 ml/l.
  • the bleaching and fixing may be conducted at a temperature of from 18° to 55° C., and preferably at 30° C. or higher. By using 35° C. or higher, the processing time may be reduced to one minute or less and the amount of the replenisher may be reduced.
  • the time required for washing after the color development or the bleaching and fixing is generally within 3 minutes. Alternatively, it is possible to use a stabilizing bath substantially without washing.
  • mildewproofing agents include 2-thiazolylbenzimidazoles as described in Japanese Patent Application (OPI) No. 157,244/82.
  • the mildewproofing agent may be either incorporated in the photosensitive material, or added from outside in the developing step, or if present in a photographic material of a processing agent, it may be added at any desired step.
  • the samples 101-106 were left in a refrigerater at ca. 5° C. for 2 weeks, and thereafter the coated layer conditions were examined. With the samples 104, 105, and 106, the separation of the couplers were obvious to the naked eyes, whereas the samples 101, 102, and 103 in which the couplers of this invention had been dispersed showed no separation of the couplers even by microscopic observation. Thus, it is evident that the couplers of this invention are excellent in solubility in organic solvents and excellent in stability on emulsifying and dispersing.
  • a film sample was prepared, which was composed of the respective layers of the following compositions on a cellulose triacetate film base.
  • sample 201 1,3-divinylsulfonyl-2-propanol as a hardener and a surfactant were added to the respective layers.
  • sample 201 1,3-divinylsulfonyl-2-propanol as a hardener and a surfactant were added to the respective layers.
  • Samples 202, 203, 204, 205, 206, 207 and 208 were prepared by the procedures similar to those for the sample 201, except that the coupler EX-1 in the first layer of the sample 201 was replaced by the equivalent molar amount of the couplers C-4, C-5, C-6, and the couplers of this invention (1), (2), (3) and (6), respectively.
  • the samples 201-208 obtained were exposed to light for sensitometry, and thereafter developed and processed using the following conditions at 38° C.
  • samples 201, 202, 205, 206, 207, and 208 obtained in Example 1 were exposed to light for sensitometry, then developed and processed in the same manner as in Example 1, except that, of the developing and processing steps of Example 1, only the bleaching solution was replaced by that of the following composition.
  • the color density was measured using red light, and the results are shown in Table 2.
  • Example 1 The film samples 201, 202, 205 and 207 obtained in Example 1 were exposed to light for sensitometry, then developed and processed in the same manner as in Example 1. Using the obtained processed samples respectively, a test on fastness of color images was conducted under the following three conditions: (i) placed in a dark place at 100° C. for 14 days, (ii) placed in a dark place at 60° C. and 70% RH for 4 weeks, and (iii) exposed to a xenon tester (100,000 lux) for 7 days. The results are shown in Table 3.
  • a multi-layered color photographic material sample was prepared, which was composed of the respective layers of the following compositions on a cellulose acetate film base, and was designated as sample 301.
  • the respective layers further contained a gelatin hardener, i.e., 1,3-divinylsulfonyl-2-propanol, a high boiling organic solvent for emulsifying and dispersing the couplers, etc. (e.g., tricresyl phosphate, dibutyl phthalate, etc.) and a surfactant.
  • a gelatin hardener i.e., 1,3-divinylsulfonyl-2-propanol
  • a high boiling organic solvent for emulsifying and dispersing the couplers, etc. e.g., tricresyl phosphate, dibutyl phthalate, etc.
  • a surfactant e.g., tricresyl phosphate, dibutyl phthalate, etc.
  • Samples were prepared in a manner similar to the above except that the coupler C-3 in the fourth layer of the sample 301 was replaced by the same molar amounts of the couplers (1) and (3) respectively, and were designated as samples 302 and 303. Furthermore, using various high boiling organic solvents for dispersing the couplers, samples 304, 305, 306 and 307 were prepared as shown in Table 4. The samples 301-307 obtained were exposed to light for sensitometry, then developed and processed in a manner similar to that in Example 2. The density was measured using red light, and the results are shown in Table 4.

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US07/245,941 1984-08-03 1988-09-19 Silver halide color photographic material Expired - Lifetime US4910128A (en)

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JP59163545A JPS6142658A (ja) 1984-08-03 1984-08-03 ハロゲン化銀カラ−写真感光材料
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Cited By (2)

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US5045442A (en) * 1990-09-27 1991-09-03 Eastman Kodak Company Photographic materials with novel cyan dye forming couplers
US5300419A (en) * 1991-05-28 1994-04-05 Fuji Photo Film Co., Ltd. Silver halide color photographic material

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JPH0799427B2 (ja) * 1986-01-28 1995-10-25 コニカ株式会社 ハロゲン化銀写真感光材料
DE69031679T2 (de) 1989-12-29 1998-06-04 Fuji Photo Film Co Ltd Farbphotographisches Silberhalogenidmaterial, das einen gelb gefärbten Cyan-Kuppler enthält
EP0440195B1 (en) 1990-01-31 1997-07-30 Fuji Photo Film Co., Ltd. Silver halide color photographic material
JPH04445A (ja) 1990-04-17 1992-01-06 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料の処理方法
EP0458131B1 (en) 1990-05-09 1997-08-06 Fuji Photo Film Co., Ltd. Photographic processing composition and processing method using the same
DE69131785T2 (de) 1990-08-20 2000-05-11 Fuji Photo Film Co., Ltd. Datenbehaltendes photographisches Filmerzeugnis und Verfahren zur Herstellung eines Farbbildes
US5525460A (en) 1992-03-19 1996-06-11 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion and light-sensitive material using the same
US5418124A (en) 1992-03-19 1995-05-23 Fuji Photo Film Co. Ltd. Silver halide photographic emulsion and a photographic light-sensitive material
JP2777949B2 (ja) 1992-04-03 1998-07-23 富士写真フイルム株式会社 ハロゲン化銀カラー写真感光材料
JP3101848B2 (ja) 1992-05-15 2000-10-23 富士写真フイルム株式会社 ハロゲン化銀カラー写真感光材料
US5407791A (en) 1993-01-18 1995-04-18 Fuji Photo Film Co., Ltd. Silver halide photographic material
EP0654705B1 (en) 1993-11-24 2000-06-21 Fuji Photo Film Co., Ltd. Photographic processing composition and method of photographic processing using the same
US5476760A (en) 1994-10-26 1995-12-19 Eastman Kodak Company Photographic emulsions of enhanced sensitivity
JP3584119B2 (ja) 1996-04-05 2004-11-04 富士写真フイルム株式会社 ハロゲン化銀カラー写真感光材料

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DE3429257A1 (de) * 1983-08-08 1985-02-28 Fuji Photo Film Co., Ltd., Minami-Ashigara, Kanagawa Farbphotographisches silberhalogenidmaterial
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US4525450A (en) * 1983-03-28 1985-06-25 Isamu Itoh Silver halide color photographic light sensitive material containing a coupler containing at least one of a sulfamoylphenylenesulfonyl, sulfamoylaminophenylenesulfonyl, or sulfoamidophenylenesulfonyl group
US4537856A (en) * 1983-04-05 1985-08-27 Konishiroku Photo Industry Co., Ltd. Method of processing silver halide color photographic materials

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US4513079A (en) * 1982-10-14 1985-04-23 Fuji Photo Film Co., Ltd. Silver halide color photographic materials
JPS59111643A (ja) * 1982-12-17 1984-06-27 Konishiroku Photo Ind Co Ltd ハロゲン化銀写真感光材料
US4518680A (en) * 1983-02-17 1985-05-21 Konishiroku Photo Industry Co., Ltd. Bleach-fixing solution and processing of light-sensitive color photographic material by use thereof
US4525450A (en) * 1983-03-28 1985-06-25 Isamu Itoh Silver halide color photographic light sensitive material containing a coupler containing at least one of a sulfamoylphenylenesulfonyl, sulfamoylaminophenylenesulfonyl, or sulfoamidophenylenesulfonyl group
US4537856A (en) * 1983-04-05 1985-08-27 Konishiroku Photo Industry Co., Ltd. Method of processing silver halide color photographic materials
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DE3429257A1 (de) * 1983-08-08 1985-02-28 Fuji Photo Film Co., Ltd., Minami-Ashigara, Kanagawa Farbphotographisches silberhalogenidmaterial

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US5045442A (en) * 1990-09-27 1991-09-03 Eastman Kodak Company Photographic materials with novel cyan dye forming couplers
US5300419A (en) * 1991-05-28 1994-04-05 Fuji Photo Film Co., Ltd. Silver halide color photographic material

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